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A new concept for control and orientation of the distribution of clean hydrocarbons produced by Fischer–Tropsch synthesis over an industrial iron catalyst

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Abstract

In this work, the performance of the Fischer–Tropsch reaction over iron catalyst in three reactor configurations was theoretically studied and analyzed. Indeed, the control and the guidance of produced hydrocarbons composition were done using a new concept of membrane separation reactor. Our findings show that the composition can be imposed by the nature of the integrated membrane. Depending on the used membrane, the water gas shift reaction equilibrium can be shifted towards hydrogen production or towards carbon monoxide production and consequently, the H2/CO ratio was changed in situ for giving olefins or paraffin according to our requirements specification. Finally, it was found that using a water permselective membrane can boost the composition to C3–C5 olefin compounds, whereas the separation of carbon dioxide can enhance the formation of paraffins.

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Abbreviations

\(A\) :

Cross-section (\({\text{m}}^{2}\))

\(C_{p}\) :

Specific heat transfer at constant pressure (\({\text{J mol}}^{ - 1} {\text{K}}^{ - 1}\))

\(C_{pg}\) :

Specific heat transfer of gaseous mixture at constant pressure (\({\text{J mol}}^{ - 1} {\text{K}}^{ - 1}\))

\(d_{p}\) :

Diameter of catalyst particle (\({\text{m}}\))

\(D_{C}\) :

Diameter of cooling tube (\({\text{m}}\))

Ð(θξ) :

Diffusivity of component \(\xi\) (\({\text{m}}^{2} {\text{s}}^{ - 1}\))

Ð0,ξ :

Diffusivity of component \(\xi\) at zero loadings and infinite temperature (\({\text{m}}^{2} {\text{s}}^{ - 1}\))

Ðθξ=0 :

Diffusivity of component \(\xi\) at zero loadings (\({\text{m}}^{2} {\text{s}}^{ - 1}\))

\(E_{5}\) :

Activation energy for paraffin formation (\({\text{J mol}}^{ - 1}\))

\(E_{5,M}\) :

Activation energy for methane formation (\({\text{J mol}}^{ - 1}\))

\(E_{6}\) :

Activation energy for olefin formation (\({\text{J mol}}^{ - 1}\))

\(E_{v}\) :

Activation energy for WGS reaction (\({\text{J mol}}^{ - 1}\))

\(E_{dif,\xi }\) :

Diffusivity activation energy of component \(\xi\) (\({\text{J mol}}^{ - 1}\))

\(F_{i}\) :

Molar flow rate of hydrocarbon \(i\) (\({\text{mol s}}^{ - 1}\))

\(F_{T}\) :

Total molar flow rate (\({\text{mol s}}^{ - 1}\))

\(F_{T}^{0}\) :

Initial molar flow rate (\({\text{mol s}}^{ - 1}\))

\(F_{IN}\) :

Molar flow rate of inert gases (\({\text{mol s}}^{ - 1}\))

\(GHSV\) :

Gas hourly space velocity (\({\text{h}}^{ - 1}\))

\({\text{I}}_{{{\text{index}}}}\) :

Fraction of inert gas

\(J_{\xi }\) :

Permeation flux of component \(\xi\) (\({\text{mol m}}^{ - 2} {\text{s}}^{ - 1}\))

\(k_{1}\) :

Rate constant of CO adsorption (\({\text{mol kg}}^{ - 1} {\text{s}}^{ - 1} {\text{bar}}^{ - 1}\))

\(k_{5}\) :

Rate constant of paraffin formation (\({\text{mol kg}}^{ - 1} {\text{s}}^{ - 1} {\text{bar}}^{ - 1}\))

\(k_{5,0}\) :

Preexponenetial factor of rate constant of paffin formation (\({\text{mol kg}}^{ - 1} {\text{s}}^{ - 1} {\text{bar}}^{ - 1}\))

\(k_{5M}\) :

Rate constant of methane formation (\({\text{mol kg}}^{ - 1} {\text{s}}^{ - 1} {\text{bar}}^{ - 1}\))

\(k_{5M,0}\) :

Pre-exponential factor of rate constant of methane formation (\({\text{mol kg}}^{ - 1} {\text{s}}^{ - 1} {\text{bar}}^{ - 1}\))

\(k_{6}\) :

Rate constant of olefin desorption reaction (\({\text{mol kg}}^{ - 1} {\text{s}}^{ - 1}\))

\(k_{6,0}\) :

Pre-exponential factor of rate constant of olefin desorption reaction (\({\text{mol kg}}^{ - 1} {\text{s}}^{ - 1}\))

\(k_{ - 6}\) :

Rate constant of olefin re-adsorption reaction (\({\text{mol kg}}^{ - 1} {\text{s}}^{ - 1} {\text{bar}}^{ - 1}\))

\(k_{v}\) :

Rate constant of \({\text{CO}}_{2}\) formation (\({\text{mol kg}}^{ - 1} {\text{s}}^{ - 1} {\text{bar}}^{ - 1.5}\))

\(k_{v,0}\) :

Pre-exponential factor of rate constant of \({\text{CO}}_{2}\) formation (\({\text{mol kg}}^{ - 1} {\text{s}}^{ - 1} {\text{bar}}^{ - 1.5}\))

\(K_{2}\) :

Equilibrium constant of \({\text{CH}}\) intermediate formation

\(K_{3}\) :

Equilibrium constant of \({\text{CH}}_{2}\) intermediate formation

\(K_{4}\) :

Equilibrium constant of \({\text{CH}}_{3}\) alkyl formation

\(K_{v}\) :

Group of constants in WGS reaction

\(K_{\xi }\) :

Adsorption equilibrium constant of component \(\xi\) (\({\text{bar}}^{ - 1}\))

\(K_{\xi ,0}\) :

Adsorption equilibrium constant of component \(\xi\) at infinite temperature (\({\text{bar}}^{ - 1}\))

\(K_{WGS}\) :

Equilibrium constant of WGS reaction

\(L\) :

Reactor length (\({\text{m}}\))

\(l\) :

Dimensionless reactor length

\(M\) :

Inlet molar flow ratio between hydrogen and carbon monoxide

\(O/P\) :

Olefin over paraffin selectivity ratio

\(P_{i}\) :

Partial pressure of hydrocarbon \(i\) (\({\text{bar}}\))

\(P_{IN}\) :

Partial pressure of inert gas (\({\text{bar}}\))

\(P_{per}\) :

Partial pressure in permeate side (\({\text{bar}}\))

\(P_{per,tot}\) :

Total pressure in permeate side (\({\text{bar}}\))

\(P_{rec}\) :

Partial pressure in reaction side (\({\text{bar}}\))

\(P_{T}\) :

Total pressure in reaction side (\({\text{bar}}\))

\(P_{T}^{0}\) :

Initial total pressure in reaction side (\({\text{bar}}\))

\(P_{\xi }\) :

Partial pressure of component \(\xi\) (\({\text{bar}}\))

\(q_{\xi }\) :

Amount adsorbed of component \(\xi \left( {{\text{mol kg}}^{ - 1} } \right)\)

\(q_{\xi }^{sat}\) :

Saturation amount adsorbed of component \(\xi \left( {{\text{mol kg}}^{ - 1} } \right)\)

\(R\) :

Universal gas constant (8.314 \({\text{J mol}}^{ - 1} {\text{K}}^{ - 1}\))

\(R_{j}\) :

Rate of reaction \(j\) (\({\text{mol kg}}^{ - 1} {\text{s}}^{ - 1}\))

\(R_{{C_{n} H_{2n + 2} }}\) :

Paraffin reaction rate (\({\text{mol kg}}^{ - 1} {\text{s}}^{ - 1}\))

\(R_{{C_{n} H_{2n} }}\) :

Olefin reaction rate (\({\text{mol kg}}^{ - 1} {\text{s}}^{ - 1}\))

\(R_{WGS}\) :

Water–gas shift reaction rate (\({\text{mol kg}}^{ - 1} {\text{s}}^{ - 1}\))

\(S_{i}\) :

Hydrocarbonsselectivity (\(\%\))

\(T\) :

Temperature (\({\text{K}}\))

\(T_{sh}\) :

Shell temperature (\({\text{K}}\))

\(U_{sh}\) :

Heat transfer coefficient shell-gases (\({\text{W m}}^{ - 2} {\text{ K}}^{ - 1}\))

\(\nu\) :

Gas linear velocity (\({\text{m s}}^{ - 1}\))

\(x\) :

Membrane coordinate

\(y\) :

Molar fraction

\(z\) :

Axial reactor coordinate

\(\varepsilon\) :

Porosity of catalytic bed

\(\varepsilon_{m}\) :

Porosity of membrane-support layer

\(\rho\) :

Catalyst density(\({\text{kg m}}^{ - 3}\))

\(\rho_{g}\) :

Gas density (\({\text{kg m}}^{ - 3}\))

\(\rho_{m}\) :

Membrane density (\({\text{kg m}}^{ - 3}\))

\(\upsilon_{ij}\) :

Stoichiometric coefficient of hydrocarbon \(i\) in reaction \(j\)

\(\mu\) :

Gas dynamic viscosity (\({\text{bar s}}^{ - 1}\))

\(\delta\) :

Membrane thickness (\({\text{m}}\))

\(\theta_{\xi }\) :

Fractional sites occupancy for component \(\xi\)

\(\Delta H_{{R_{j} }}\) :

Enthalpy of reaction \(j\) (\({\text{J mol}}^{ - 1}\))

\(\Delta H_{ads, {\xi}}\) :

Adsorption enthalpy of component \(\xi\) (\({\text{J mol}}^{ - 1}\))

\(g\) :

Gas-phase

\(i\) :

Index indicating hydrocarbons

\(IN\) :

Inert gases

\(j\) :

Index indicating reactions

\(m\) :

Membrane

\(n\) :

Chain length of hydrocarbons

\(0\) :

Inlet reactor

\(BTL\) :

Biomass to liquid

\(CTL\) :

Coal to liquid

\(CR\) :

Conventional reactor

\(FT\) :

Fischer–Tropsch

\(GTL\) :

Gas To liquid

\(MRC\) :

Membrane reactor for carbon dioxide removal

\(MRW\) :

Membrane reactor for water removal

\(WGS\) :

Water–gas-shift

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  1. Laboratory of Chemical Processes Engineering, Department of Processes Engineering, Faculty of Technology, Ferhat Abbas University of Setif 1, 19000, Setif, Algeria

    Abdelmalek Bellal & Lemnouer Chibane

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  1. Abdelmalek Bellal
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Correspondence to Abdelmalek Bellal.

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Bellal, A., Chibane, L. A new concept for control and orientation of the distribution of clean hydrocarbons produced by Fischer–Tropsch synthesis over an industrial iron catalyst. Reac Kinet Mech Cat 129, 725–742 (2020). https://doi.org/10.1007/s11144-020-01726-7

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  • DOI: https://doi.org/10.1007/s11144-020-01726-7

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